Spatial distribution of major and trace elements in artificial lakes in Serbia: health risk indices and suitability of water for drinking and irrigation purposes.

Lakes and reservoirs are the main water resources for household, irrigation, and industrial use. Hence, it is necessary to control water pollution and have reliable information on water quality, which refers to its suitability for a particular purpose. The main objective of this study was to evaluate the suitability of water for drinking and irrigation purposes from ten artificial lakes on the territory of the Republic of Serbia. The physicochemical parameters were determined using standard analytical methods, whereas the optical emission spectrometry with inductively coupled plasma, ICP-OES, was used to determine the concentrations of 23 macro-, micro-, and trace elements in water. Health risk indices of drinking water and its suitability for irrigation purposes were evaluated. The results of physicochemical parameters, except for total organic matter, indicated that most samples were within the recommended values. Among analyzed elements, the concentration of Mg was elevated in the water of the lakes Srebrno and Prvonek. The results of health risk assessment clearly showed that there was no acute health risk (HQA < 1), whereas long-term risk (HQL) in the studied lakes was observed with respect to As (lakes Grliste and Srebrno), Mn (lakes Srebrno and Prvonek), Ni (Lake Vrutci), and Sr (Lake Grliste). The irrigation criteria indicated that the water from the examined lakes had satisfactory quality for this purpose, except for residual sodium carbonates (RSC). This criterion indicated low quality or unsuitability of the water in 7 lakes. The main outcomes provided valuable information on the suitability of water from the artificial lakes for intended uses.

Alkaline soda Lake Velika Rusanda (Serbia): the first insight into diatom diversity of this extreme saline lake.

Alkaline soda lakes are unique habitats found in specific geographic regions, usually with dry climate. The Carpathian Basin is one of those regions very important for habitat and biodiversity conservation in Europe, with natural soda lakes found in Austria, Hungary and Serbia. In comparison to other two countries from Central Europe, algal biodiversity studies of saline soda lakes in Serbia are scarce. Lake Velika Rusanda has the highest measured salinity of all saline lakes in the Carpathian Basin and there were no reports of its diatom species richness and diversity till now. We conducted 2-year investigation programme to study biodiversity and seasonal dynamics of diatoms in this lake. A total of 27 diatom taxa were found, almost all of them attached to reed and much less in benthos and plankton. Five new diatom species for Serbia were recorded, Craticula halopannonica, Navicymbula pusilla, Hantzschia weyprechtii, Nitzschia thermaloides and Navicula staffordiae. The last mentioned is new for Europe as well. Lake Velika Rusanda is inhabited mostly by alkaliphilous and halophilic diatoms. Since diatoms are used as bioindicators in soda lakes, our results will improve their further application in ecological status assessment of these fragile habitats in the Carpathian Basin.

Differently shaped nanocrystalline (Fe, Y)3O4 and its adsorption efficiency toward inorganic arsenic species.

Herein we report effects of partial substitution of Fe3+ by Y3+ in magnetite (Fe3O4) on morphology and inorganic arsenic species adsorption efficiency of the Fe3-x Y x O4 nanoparticles formed. The series of Fe3-x Y x O4 (x = 0.00, 0.042 and 0.084, labeled as Y00, Y05 and Y10, respectively) was synthesized using co-precipitation followed by microwave-hydrothermal treatment (MW) at 200 °C. With increase of yttrium content (x value), both the morphological inhomogeneity of the samples and the fraction of spinel nanorods as compared to spinel pseudospherical particles increased. By both transmission electron microscopy and x-ray powder diffraction analyses, it was determined that the direction of growth of the spinel nanorods is along the [110] crystallographic direction. The Fe3-x Y x O4 affinities of adsorption toward the inorganic arsenic species, As(III) (arsenite, AsO3 3-) and As(V) (arsenate, AsO4 3-), were investigated. Increased Y3+ content related to changes in sample morphology was followed by a decrease of As(III) removal efficiency and vice versa for As(V). The increase in Y3+ content, in addition to increasing the adsorption capacity for As(V), significantly expanded the optimum pH range for the maximum removal and decreased the contact time for necessary 50% removal (t 1/2) of As(V) (Y00: pH 2-3, t 1/2 = 3.12 min; Y05: pH 2-6, t 1/2 = 2.12 min and Y10: pH 2-10, t 1/2 = 1.12 min). The results point to incorporation of Y3+ in the crystal lattice of magnetite, inducing nanorod spinel structure formation with significant changes in sorption properties important for the removal of inorganic arsenic from waters.

Assessment of spa mineral water quality from Vrnjacka Banja, Serbia: geochemical, bacteriological, and health risk aspects.

The goal of this study is to evaluate the quality of seven natural mineral water sources in the Vrnjacka Banja area used in the treatment of various diseases. The 24 macro- and microelements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The results show that element content was within allowed limits of concentration, except for B, As, and Se. The evaluated content of these elements can be associated with geological and anthropogenic factors. The sample S6 contains more than twice the concentration of As, meaning that the use of water from this source should be limited due to the negative impact of this element on human health. The calculated values of weekly (EWI) and oral (OI) intakes as well as the acute hazard quotient (HQA) of selected toxic and potentially toxic elements indicate no health risks to the consumers. The highest hazard quotient (HQL) observed for As in sample S6 (2.0·10-1) demonstrated a significant risk of carcinogenic diseases in long-term consumption from this source. The estimated non-carcinogenic (DIA) and carcinogenic (DIL) dermal intakes with acute (HQA) and long-term (HQL) hazard quotient values for sample S3 show that there is no health risk to those who use the water from this thermal source for bathing. The presence of aerobic mesophilic bacteria at 22 °C and 37 °C in samples S3, S6, and S7 as well as sulphite-reducing Clostridia species in sample S5 were detected, potentially indicating some non-faecal or faecal contamination.

Individual effects of different selenocompounds on the hepatic proteome and energy metabolism of mice.

BACKGROUND: Selenium (Se) exerts its biological activity largely via selenoproteins, which are key enzymes for maintaining the cellular redox homeostasis. However, besides these beneficial effects there is also evidence that an oversupply of Se might increase the risk towards developing metabolic disorders. To address this in more detail, we directly compared effects of feeding distinct Se compounds and concentrations on hepatic metabolism and expression profiles of mice. METHODS: Male C57BL6/J mice received either a selenium-deficient diet or diets enriched with adequate or high doses of selenite, selenate or selenomethionine for 20weeks. Subsequently, metabolic parameters, enzymatic activities and expression levels of hepatic selenoproteins, Nrf2 targets, and additional redox-sensitive proteins were analyzed. Furthermore, 2D-DIGE-based proteomic profiling revealed Se compound-specific differentially expressed proteins. RESULTS: Whereas heterogeneous effects between high concentrations of the Se compounds were observed with regard to body weight and metabolic activities, selenoproteins were only marginally increased by high Se concentrations in comparison to the respective adequate feeding. In particular the high-SeMet group showed a unique response compromising higher hepatic Se levels in comparison to all other groups. Accordingly, hepatic glutathione (GSH) levels, glutathione S-transferase (GST) activity, and GSTpi1 expression were comparably high in the high-SeMet and Se-deficient group, indicating that compound-specific effects of high doses appear to be independent of selenoproteins. CONCLUSIONS: Not only the nature, but also the concentration of Se compounds differentially affect biological processes. GENERAL SIGNIFICANCE: Thus, it is important to consider Se compound-specific effects when supplementing with selenium.

Preliminary investigation of mineral content of pollen collected from different Serbian maize hybrids - is there any potential nutritional value?

BACKGROUND: Bee pollen has already proved to be a good supplement rich in iron and zinc. Studies on the application of flower pollen in the food industry and medicine have begun. Bearing in mind the prevalence of maize as a crop culture, its pollen will be easily available. The mineral composition of pollen of seven Serbian maize hybrids was analyzed in order to establish its nutritional value and the benefits of its implementation in the human diet using the inductively coupled plasma method. RESULTS: The presence of twenty four different macro- (nine) and micronutrients (fifteen) was detected. The most common minerals were phosphorus and potassium, while arsenic, cobalt, lead, nickel and molybdenum were found in some samples. CONCLUSION: Comparing the results obtained with recommended or tolerable dietary intake references for adults, it was found that maize pollen can be used as a very good source of zinc, iron, chromium and manganese for humans. With regard to selenium content, pollen samples proved to be moderately good source of this important micronutrient. Contents of some elements (Fe, Zn, Mn, Cr, Se, Al and V) showed significant differences depending on hybrid type. In some samples increased concentrations of aluminum and vanadium were recorded, which may pose a potential problem due to their toxicity. © 2016 Society of Chemical Industry.

Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity.

A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(µ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl3(µ-ox)(NO)}4](5-) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2-5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d-4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2-5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d-4f metal complexes 6-9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 µM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells.

Arsenic in drinking water and acute coronary syndrome in Zrenjanin municipality, Serbia.

BACKGROUND: Arsenic is constantly present in drinking water supply systems of Zrenjanin municipality across decades. It presents a great public health problem in Serbia, but its relationship with acute coronary syndrome (ACS) has not been studied previously. OBJECTIVES: The aims of this study were to assess the incidence of ACS in two areas from Zrenjanin municipality consuming different levels of arsenic in drinking water, and to explore the association between arsenic exposure and the probability of fatal outcome of ACS. METHODS: The research was a registry-based ecological study of two populations consuming water with different arsenic levels, based on current guidelines (10 µg/L). Median arsenic in the area above national standard was 80 µg/L; median arsenic in the other area was 1 µg/L. Newly diagnosed cases of ACS were obtained from the National Registry for Acute Coronary Syndrome from 2006 to 2010. RESULTS: The two populations were comparable by age, gender, and prevalence of risk factors for ACS. Standardized incidence rates (SIR) of ACS were higher for people consuming arsenic above standard (average five-year SIR was 237.00 per 100.000; 95% CI=214.93-260.74), in comparison to people consuming arsenic within limits (average SIR=124.40 per 100.000; 95% CI=96.00-158.56). Exposure to arsenic above limits was insignificantly associated with fatal outcome of ACS for the whole population, men and women. CONCLUSIONS: Consumption of arsenic above national standards was associated with higher risk for the occurrence of acute coronary syndrome and with insignificantly higher probability of fatal outcome of ACS in Zrenjanin municipality.

Cell cycle, apoptosis, cellular uptake and whole-transcriptome microarray gene expression analysis of HeLa cells treated with a ruthenium(II)-arene complex with an isoquinoline-3-carboxylic acid ligand.

Ruthenium(II)-arene complexes are promising drug candidates for the therapy of solid tumors. In previous work, seven new compounds of the general formula [Ru(η6-p-cymene)(L1-7)Cl] were synthesized and characterized, of which the complex with L=isoquinoline-3-carboxylic acid (RuT7) was two times as active on HeLa cells compared to normal cell line MRC-5, as indicated by IC50 values determined after 48h of incubation (45.4±3.0 vs. 84.2±5.7µM, respectively). In the present study, cell cycle analysis of HeLa cells treated with RuT7 showed S phase arrest and an increase in sub-G1 population. The apoptotic potential of the title compound was confirmed with the Annexin V-FITC/PI assay together with a morphological evaluation of cells using fluorescent microscopy. Analysis of the intracellular accumulation of ruthenium showed 8.9ng Ru/106 cells after 6h of incubation. To gain further insight in the molecular mechanism of action of RuT7 on HeLa cells, a whole-transcriptome microarray gene expression analysis was performed. Analysis of functional categories and signaling and biochemical pathways associated with the response of HeLa cells to treatment with RuT7 showed that it leads the cells through the intrinsic (mitochondrial) apoptotic pathway, via indirect DNA damage due to the action of reactive oxygen species, and through direct DNA binding of RuT7. Statistical analysis for enrichment of gene sets associated with known drug-induced toxicities identified fewer associated toxicity profiles in RuT7-treated cells compared to cisplatin treatment. Altogether these results provide the basis for further development of RuT7 in animal and pre-clinical studies as a potential drug candidate.

Mineral content of bee pollen from Serbia.

In this study we analysed mineral composition of bee pollen of different plant origin collected across Serbia using inductively coupled plasma - optical emission spectrometry. The most abundant elements were potassium, calcium, and magnesium. The samples were also exceptionally rich in iron and zinc, which are very important as nutrients. Judging by our findings, mineral composition of bee pollen much more depends on the type of pollen-producing plant than on its geographical origin.

Chemical composition of two different extracts of berries harvested in Serbia.

Total phenolic content (TPC), total anthocyanin content (TAC), free and total ellagic acid content, sugars, minerals, and radical-scavenging activity were determined in nine berries harvested in Serbia. More than 30 phenolic compounds were identified; among them, 11 polyphenols and cis,trans-abscisic acid were quantified using UHPLC coupled with an LTQ-Orbitrap XL mass analyzer. For the first time chrysin, naringenin, pinocembrin, and galangin were quantified in some of the investigated berry species. The extraction efficiency of the two extraction systems, methanol and acetone, was investigated. It was found that acetone is a better extracting solvent for TPC, whereas more TAC was extracted by methanol. TPC in acetone extracts ranged from 177.51 to 459.71 mg gallic acid equiv/100 g frozen weight. TAC ranged from 5.39 to 96.94 mg cyanidin-3-glucoside/100 g frozen weight in methanol extracts. The amounts of both free and total ellagic acid were found to be higher in the acetone extract in comparison to the methanol extract.

Decolorization of reactive textile dyes using water falling film dielectric barrier discharge.

Decolorization of reactive textile dyes Reactive Black 5, Reactive Blue 52, Reactive Yellow 125 and Reactive Green 15 was studied using advanced oxidation processes (AOPs) in a non-thermal plasma reactor, based on coaxial water falling film dielectric barrier discharge (DBD). Used initial dye concentrations in the solution were 40.0 and 80.0mg/L. The effects of different initial pH of dye solutions, and addition of homogeneous catalysts (H(2)O(2), Fe(2+) and Cu(2+)) on the decolorization during subsequent recirculation of dye solution through the DBD reactor, i.e. applied energy density (45-315kJ/L) were studied. Influence of residence time was investigated over a period of 24h. Change of pH values and effect of pH adjustments of dye solution after each recirculation on the decolorization was also tested. It was found that the initial pH of dye solutions and pH adjustments of dye solution after each recirculation did not influence the decolorization. The most effective decolorization of 97% was obtained with addition of 10mM H(2)O(2) in a system of 80.0mg/L Reactive Black 5 with applied energy density of 45kJ/L, after residence time of 24h from plasma treatment. Toxicity was evaluated using the brine shrimp Artemia salina as a test organism.